Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/13—Morphological aspects
  • C08G2261/135—Cross-linked structures
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
  • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
  • C08G2261/3162—Arylamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
  • C08G2261/41—Organometallic coupling reactions
  • C08G2261/411—Suzuki reactions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/50—Physical properties
  • C08G2261/51—Charge transport
  • C08G2261/512—Hole transport
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/70—Post-treatment
  • C08G2261/76—Post-treatment crosslinking

Definitions

• the present invention relates to a method for producing a polymer compound.
• a polymer compound is used as a material for an organic electroluminescence element or the like.
• the polymer compound has a low content of a low molecular weight compound and a low polydispersity (Mw / Mn).
• the polymer compound can be synthesized, for example, by subjecting an aromatic diboronic acid and an aromatic dihalide to a Suzuki coupling reaction in the presence of a transition metal complex.
• Non-Patent Document 1 reports a method of synthesizing a fluorene diboronic acid and a tribromoamine dibromo compound by a Suzuki coupling reaction.
• this method it has been difficult to obtain a polymer compound having a sufficiently low polydispersity.
• An object of the present invention is to provide a method for producing a polymer compound having a crosslinkable group with a low content of a low molecular weight compound and a sufficiently low polydispersity.
• the present invention provides the following [1] to [10].
• [1] A method for producing a polymer compound having a crosslinkable group, (1) A step of obtaining a first polymer compound having a crosslinkable group by polymerizing a monomer component in a solvent in the presence of a transition metal complex, wherein the monomer component is crosslinkable. Including a monomer having a group, and (2) A polymer having the largest polystyrene-equivalent weight average molecular weight after mixing a solution containing the first solvent and the first polymer compound and the second solvent and then separating the mixture into two or more layers.
• a method for producing a polymer compound comprising: [2] The monomer component is a compound represented by the formula (1) and a compound represented by the formula (2), and The first polymer compound and the second polymer compound are polymer compounds each including a structural unit represented by the formula (3) and a structural unit represented by the formula (4). [1] A process for producing the polymer compound according to [1]. [Where: a and b each independently represents an integer of 0 to 2.
• Ar 1 , Ar 2 , Ar 4 and Ar 5 are each independently a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or a divalent aromatic hydrocarbon group and a divalent heterocyclic group. Represents a bonded group, and these groups may have a substituent. When a plurality of Ar 2 or Ar 5 are present, they may be the same or different.
• Ar 3 and Ar 6 each independently represent a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group, and these groups optionally have a substituent. When a plurality of Ar 3 or Ar 6 are present, they may be the same or different.
• Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 or Ar 6 has a group containing a crosslinkable group as a substituent.
• X 1 represents a chlorine atom, a bromine atom, an iodine atom, or —O—S ( ⁇ O) 2 R a1 .
• R a1 represents an alkyl group or an aryl group, and these groups optionally have a substituent.
• a plurality of X 1 may be the same or different.
• X 2 represents —B (OH) 2 , a borane residue, a borate ester residue, or —BF 3 T.
• T represents a lithium atom, a sodium atom, a potassium atom, a rubidium atom, or a cesium atom.
• a plurality of X 2 may be the same or different.
• [3] The method for producing a polymer compound according to [2], wherein the group containing the crosslinkable group is a group represented by the formula (5). [Where: L is each independently a single bond, or — (CH 2 ) —, —O—, —S—, — (CO) —, — (C 6 H 4 ) —, or two or more selected from these Represents a divalent group to which the group is bonded.
• n an integer of 1 to 5.
• Y represents a crosslinkable group. When a plurality of Y are present, they may be the same or different.
• L is — (CH 2 ) m —, — (CH 2 ) p — (C 6 H 4 ) — (CH 2 ) q —, — (CH 2 ) r —O— (CH 2 ) s —, or — (CH 2 ) t — (C 6 H 4 ) —O— (CH 2 ) u —
• m represents an integer of 0 to 20
• p represents an integer of 0 to 10
• q represents an integer of 0 to 10
• r represents an integer of 0 to 10
• s represents an integer of 0 to 10
• t represents an integer of 0 to 10
• u represents an integer of 0 to 10
• n XL represents an integer of 0 to 5. When a plurality of n XL are present, they may be the same or different.
• R XL represents — (CH 2 ) —, —O—, —S— , — (CO) —, or a divalent group in which two or more groups selected from these are bonded.
• —O—s, —S—s, and —O— and —S— are not directly bonded to each other.
• R XL When a plurality of R XL are present, they may be the same or different.
• the transition metal complex is At least one ligand selected from the group consisting of trialkylphosphine, dialkylmonoarylphosphine, monoalkyldiarylphosphine, and triarylphosphine (the aryl groups on the phosphine are each independently an alkyl group, an alkoxy group, A phenyl group (the phenyl group may have 1 to 3 substituents selected from the group consisting of alkyl groups and alkoxy groups), and 1 to 3 groups selected from the group consisting of substituted amino groups May have a substituent), A palladium complex containing palladium, [1] The production method according to any one of [5].
• the method of the present invention it is possible to produce a polymer compound having a crosslinkable group with a low content of a low molecular weight compound and a sufficiently low polydispersity. Moreover, according to the method of the present invention, the polydispersity of the polymer compound having a crosslinkable group obtained by polymerization can be drastically reduced.
• Halogen atom means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• Alkyl group means a linear, branched or cyclic alkyl group.
• the number of carbon atoms in the linear alkyl group is usually 1 to 50, preferably 3 to 30, and more preferably 4 to 20.
• the number of carbon atoms in the branched and cyclic alkyl group is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.
• alkyl group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isoamyl, 2-ethylbutyl, n- Hexyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, cyclohexylethyl group, n-octyl group, 2-ethylhexyl group, 3-n-propylheptyl group, n-decyl group, 3,7-dimethyloctyl group, Examples include 2-ethyloctyl group, 2-n-hexyl-decyl group, n-dodecyl group and the like.
• the “alkyl group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, and an aryl group (the aryl group is a group consisting of an alkyl group and an alkoxy group). And a monovalent heterocyclic group, an alkoxy group, an aryloxy group, a substituted amino group, and the like.
• the “alkyl group” may have 1 to 20 substituents selected from these substituents.
• Examples of the substituted alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, and a 3- (4-methylphenyl) propyl group. , 3- (3,5-di-n-hexylphenyl) propyl group, 6-ethyloxyhexyl group and the like.
• Alkylene group means a divalent group obtained by removing one hydrogen atom from the “alkyl group”. Examples of the alkylene group include a dimethylene group and a trimethylene group.
• the “alkylene group” may have a substituent, and the alkylene group is selected from the group consisting of a halogen atom (particularly a fluorine atom), a cyano group, and an aryl group (the aryl group is an alkyl group and an alkoxy group).
• the “alkylene group” may have 1 to 20 substituents selected from these substituents.
• Aryl group means a monovalent group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.
• the number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 20, and more preferably 6 to 10.
• Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, and a 4-pyrenyl group. 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group and the like.
• the “aryl group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, an alkyl group, and an aryl group (the aryl group includes an alkyl group and an alkoxy group).
• the “aryl group” may have 1 to 10 substituents selected from these substituents.
• the substituted aryl group include a 2-phenylphenyl group, a 3-phenylphenyl group, and a 4-phenylphenyl group.
• Alkoxy group means a linear, branched or cyclic alkoxy group.
• the straight-chain alkoxy group usually has 1 to 40 carbon atoms, preferably 4 to 10 carbon atoms.
• the number of carbon atoms in the branched and cyclic alkoxy group is usually 3 to 40, preferably 4 to 10.
• alkoxy group examples include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, Examples include cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group and the like.
• the “alkoxy group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, and an aryl group (the aryl group is a group consisting of an alkyl group and an alkoxy group). And a monovalent heterocyclic group, an alkoxy group, an aryloxy group, a substituted amino group, and the like.
• the “alkoxy group” may have 1 to 10 substituents selected from these substituents.
• Aryloxy group means a monovalent group in which one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon is replaced with an oxygen atom.
• the number of carbon atoms of the aryloxy group is usually 6 to 60, preferably 7 to 48.
• Examples of the aryloxy group include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1-pyrenyloxy group and the like.
• the “aryl” in the “aryloxy group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, an alkyl group, and the aryl group is an alkyl group. And optionally having 1 to 3 substituents selected from the group consisting of alkoxy groups), monovalent heterocyclic groups, alkoxy groups, aryloxy groups, substituted amino groups, and the like.
• the “aryl” may have 1 to 10 substituents selected from these substituents. Examples of the substituted aryloxy group include 2-phenylphenoxy group, 3-phenylphenoxy group, 4-phenylphenoxy group and the like.
• “Substituted amino group” means an amino group having two substituents.
• the substituent include an alkyl group and an aryl group (the aryl group may have 1 to 3 substituents selected from the group consisting of an alkyl group and an alkylene group), a monovalent complex A cyclic group etc. are mentioned.
• the substituted amino group include a dialkylamino group, a diarylamino group, and a di (mono or dialkylaryl) amino group.
• Specific examples include a dimethylamino group, a diethylamino group, a diphenylamino group, and a bis ( 4-methylphenyl) amino group, bis (4-tert-butylphenyl) amino group, bis (3,5-di-tert-butylphenyl) amino group and the like.
• a monovalent aromatic hydrocarbon group means a monovalent group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.
• the number of carbon atoms of the aromatic hydrocarbon is usually 6 to 60, preferably 6 to 20, and more preferably 6 to 10.
• Examples of the monovalent aromatic hydrocarbon group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, and 2-pyrenyl. Group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group and the like.
• the “monovalent aromatic hydrocarbon group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, an alkyl group, and an aryl group (the aryl group is , Optionally having 1 to 3 substituents selected from the group consisting of alkyl groups and alkoxy groups), monovalent heterocyclic groups, alkoxy groups, aryloxy groups, substituted amino groups, alkylene groups (dimethylene) Group, trimethylene group, etc.).
• the “monovalent aromatic hydrocarbon group” may have 1 to 10 substituents selected from these substituents.
• the substituted monovalent aromatic hydrocarbon group include a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and a benzocyclobutenyl group.
• the “divalent aromatic hydrocarbon group” is selected from the group consisting of a divalent group obtained by removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon, and the divalent group. Means a divalent group in which a plurality of (for example, 2 to 5) are bonded.
• the number of carbon atoms of the divalent aromatic hydrocarbon group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18.
• divalent aromatic hydrocarbon group examples include phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrene diyl group, dihydrophenanthenediyl group, naphthacene diyl group, fluorenediyl group, pyrenediyl group, perylene diyl group, chrysenediyl group.
• the “divalent aromatic hydrocarbon group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, an alkyl group, an aryl group (the aryl group is , Optionally having 1 to 5 substituents selected from the group consisting of an alkyl group, an alkoxy group, a phenyl group and an alkylphenyl group), a monovalent heterocyclic group, an alkoxy group, an aryloxy group, a substituted group An amino group, an alkylene group (dimethylene group, trimethylene group, etc.) etc. are mentioned.
• the divalent aromatic hydrocarbon group may have 1 to 10 substituents selected from these substituents. Examples of the divalent aromatic hydrocarbon group which may have the substituent include groups represented by formulas (A-1) to (A-20).
• R and R a are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group (the aryl group is selected from the group consisting of an alkyl group, an alkoxy group, a phenyl group, and an alkylphenyl group. And a monovalent heterocyclic group, an alkoxy group, an aryloxy group, or a substituted amino group.
• a plurality of R and R a may be the same or different. Adjacent R a may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. ]
• examples of the group in which the two R a are bonded to each other include, for example, an alkylene group, 2,2′-biphenylene Group (the 2,2′-biphenylene group may have 1 to 5 alkyl groups) and the like.
• the “p-valent heterocyclic group” (p represents an integer of 1 or more, and in particular, p is 1 or 2) means that a heterocyclic compound is directly bonded to a carbon atom or a hetero atom constituting the ring. This means a p-valent group in which p hydrogen atoms are removed from the bonded hydrogen atoms.
• p-valent heterocyclic groups it is a p-valent group obtained by removing p hydrogen atoms from a hydrogen atom directly bonded to a carbon atom or a hetero atom constituting a ring from an aromatic heterocyclic compound.
• a “p-valent aromatic heterocyclic group” is preferable.
• ⁇ aromatic heterocyclic compound '' for example, oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzosilole, A compound in which the heterocycle itself is aromatic, such as dibenzophosphole; a heterocycle such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, benzopyran does not exhibit aromaticity, but the heterocycle has an aromatic ring A compound having a condensed ring; and a compound in which a plurality of these compounds are bonded to each other are meant.
• the number of carbon atoms of the “p-valent heterocyclic group” is usually 2 to 60, preferably 3 to 20.
• the “p-valent heterocyclic group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, an alkyl group, and an aryl group (the aryl group is an alkyl group). 1 to 5 substituents selected from the group consisting of a group, an alkoxy group, a phenyl group and an alkylphenyl group), a monovalent heterocyclic group, an alkoxy group, an aryloxy group, a substituted amino group And alkylene groups (dimethylene group, trimethylene group, etc.).
• the “p-valent heterocyclic group” may have 1 to 10 substituents selected from these substituents.
• Examples of the “monovalent heterocyclic group” include thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group and the like.
• the “monovalent heterocyclic group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, an alkyl group, and an aryl group (the aryl group is an alkyl group). 1 to 5 substituents selected from the group consisting of a group, an alkoxy group, a phenyl group and an alkylphenyl group), a monovalent heterocyclic group, an alkoxy group, an aryloxy group, a substituted amino group And alkylene groups (dimethylene group, trimethylene group, etc.).
• the monovalent heterocyclic group may have 1 to 5 substituents selected from these substituents.
• divalent heterocyclic group examples include pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilole, phenoxazine, phenothiazine, acridine, dihydroacridine, furan, thiophene, Two of the hydrogen atoms directly bonded to the carbon atom or hetero atom constituting the ring from aromatic heterocyclic compounds such as azole, diazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, etc. And a divalent group in which a plurality (for example, 2 to 4) selected from the group consisting of the divalent group and the divalent group removed are bonded.
• the “divalent heterocyclic group” may have a substituent.
• the substituent include a halogen atom (particularly a fluorine atom), a cyano group, an alkyl group, and an aryl group (the aryl group is an alkyl group). 1 to 5 substituents selected from the group consisting of a group, an alkoxy group, a phenyl group and an alkylphenyl group), a monovalent heterocyclic group, an alkoxy group, an aryloxy group, a substituted amino group And alkylene groups (dimethylene group, trimethylene group, etc.).
• the divalent heterocyclic group may have 1 to 5 substituents selected from these substituents.
• the divalent heterocyclic group which may have the substituent is preferably a group represented by the formula (A-21) to the formula (A-52).
• R and R a represent the same meaning as described above.
• R ′ represents an alkyl group, an aryl group (the aryl group may have 1 to 5 substituents selected from the group consisting of an alkyl group, an alkoxy group, a phenyl group, and an alkylphenyl group), or Represents a monovalent heterocyclic group. When a plurality of R ′ are present, they may be the same or different.
• the “group in which a divalent aromatic hydrocarbon group and a divalent heterocyclic group are bonded” includes one or more of the above-described divalent aromatic hydrocarbon groups and the above-mentioned divalent heterocycle. It means a divalent group in which one or more of the cyclic groups are arbitrarily bonded. What was mentioned above is mentioned as a bivalent aromatic hydrocarbon group and a bivalent heterocyclic group.
• the “group in which a divalent aromatic hydrocarbon group and a divalent heterocyclic group are bonded” may have a substituent, and a divalent aromatic hydrocarbon group and / or a partial structure thereof.
• a part or all of the divalent heterocyclic group includes a halogen atom, a cyano group, an alkyl group, an aryl group (the aryl group is selected from the group consisting of an alkyl group, an alkoxy group, a phenyl group, and an alkylphenyl group).
• the above-described halogen atom, cyano group, alkyl group, aryl group (the aryl group is an alkyl group, an alkoxy group) , Phenyl group and alkyl 1 may be substituted with 1 to 5 substituents selected from the group consisting of a phenyl group) and 1 selected from a monovalent heterocyclic group, an alkoxy group, an aryloxy group, a substituted amino group, and an alkylene group. It may have up to 5 substituents.
• the method for producing a polymer comprises: (1) A step of obtaining a first polymer compound having a crosslinkable group by polymerizing a monomer component in a solvent in the presence of a transition metal complex, wherein the monomer component is crosslinkable. Including a monomer having a group, and (2) a solution containing a first solvent and the first polymer compound, and a second solvent are mixed, and then separated into two or more layers.
• a step of obtaining a second polymer compound having a crosslinkable group by selecting a layer containing a polymer compound having the largest polystyrene-equivalent weight average molecular weight, wherein the first solvent is in step (1)
• the second solvent is a poor solvent for the first polymer compound, and the solvent contained in each of the two or more layers is substantially an organic solvent.
• Step (1) is a step of obtaining a first polymer compound having a crosslinkable group by polymerizing a monomer component containing a monomer having a crosslinkable group in a solvent in the presence of a transition metal complex. It is.
• step (1) it is preferable to polymerize a monomer component including a monomer having a crosslinkable group after reducing the oxygen concentration in the reaction vessel by inert gas replacement.
• a monomer component including a monomer having a crosslinkable group After the polymerization reaction starts, if necessary, at least one selected from the group consisting of monomer components including a transition metal complex, a solvent, and a monomer having a crosslinkable group may be further added to the reaction system. Good.
• step (1) a base and a phase transfer catalyst may be used as necessary to promote the reaction.
• the transition metal complex is used as a catalyst for polymerizing (coupling reaction) a monomer component including a monomer having a crosslinkable group.
• the compound represented by the formula (1) and the compound represented by the formula (2) are used as a catalyst for polymerizing each other.
• a Group 10 transition metal complex is preferable, and a palladium complex is more preferable.
• the group 10 transition metal complex is preferably a zero-valent group 10 transition metal complex or a divalent group 10 transition metal complex, and more preferably a divalent group 10 transition metal complex.
• the palladium complex may be a homogeneous palladium complex or a heterogeneous palladium complex, and is preferably a homogeneous palladium complex.
• the ligand possessed by the transition metal complex is not particularly limited as long as it can coordinate to a transition metal (particularly palladium).
• the ligand include a ligand having an atom or an atomic group such as a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a carbon-carbon unsaturated bond, a carbene, a carbon monoxide, and a halogen atom. Any of a ligand or a polydentate ligand (bidentate ligand, tridentate ligand, etc.) may be used.
• phosphine ligands are preferred, trialkylphosphine ligands, dialkylmonoarylphosphine ligands, monoalkyldiarylphosphine ligands, triarylphosphine ligands are more preferred, dialkylarylphosphine ligands, More preferred are triarylphosphine ligands.
• the aryl group on the phosphine ligand is independently an alkyl group, an alkoxy group, or a phenyl group (the phenyl group has 1 to 3 substituents selected from the group consisting of an alkyl group and an alkoxy group). And 1 to 3 substituents selected from the group consisting of substituted amino groups.
• the transition metal complex is preferably a palladium complex, and specific examples thereof include dichlorobis (triphenylphosphine) palladium, dichlorobis (tricyclohexylphosphine) palladium, dichlorobis [tris (2-methylphenyl) phosphine] palladium, dichlorobis [tris (2-methoxy).
• the transition metal complex may be used alone or in combination of two or more.
• transition metal complexes triphenylphosphine, tri (tert-butylphosphine), tricyclohexylphosphine, 1,3-bis (diphenylphosphino) propane, 1,1′-bis (diphenylphosphino)
• a new transition metal (for example, palladium) complex can also be formed in the reaction system in the presence of a ligand different from the ligand of the complex such as ferrocene and bipyridyl.
• the solvent used in the step (1) is not particularly limited as long as it can dissolve the first polymer compound having a crosslinkable group to be generated, that is, a good solvent for the first polymer compound.
• the solvent (good solvent for the first polymer compound) can be selected from various solvents according to the characteristics of the first polymer compound. Specifically, it can be defined as a solvent in which the solubility (20 ° C.) of the first polymer compound is 1 g / 100 g or more.
• the solvent examples include aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, cyclohexylbenzene, and tetralin; ether solvents such as tetrahydrofuran, 1,4-dioxane, dimethoxyethane, and anisole; N, N-dimethylacetamide, N, Amide solvents such as N-dimethylformamide and N-methyl-2-pyrrolidone; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; Acetone, methyl ethyl ketone and cyclopenta Ketone solvents such as non, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; ace
• the solvent is preferably an aromatic hydrocarbon solvent or an ether solvent, and more preferably an aromatic hydrocarbon solvent.
• the number of carbon atoms in the aromatic hydrocarbon solvent is preferably 6-12, more preferably 7-9.
• the aromatic hydrocarbon solvent is preferably toluene, xylene and mesitylene.
• the ether solvent may be any of linear, branched and cyclic ether solvents, but is preferably a cyclic ether solvent.
• the ether solvent preferably has 4 to 7 carbon atoms.
• the ether solvent is preferably tetrahydrofuran.
• the amount of the solvent used is usually 100 to 100,000 g, preferably 500 to 20000 g, per 1 mol of the total amount of monomer components of the raw material.
• the base is not particularly limited as long as it promotes the coupling reaction (polymerization reaction) in step (1).
• the base may be either an inorganic base or an organic base, and is preferably an organic base.
• a base may be used individually by 1 type, or may use 2 or more types together.
• Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal phosphates such as potassium phosphate.
• organic base examples include tetraalkylammonium hydroxide, tetraalkylammonium carbonate, tetraalkylammonium dicarbonate, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5. 4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, dimethylaminopyridine, pyridine, trialkylamine, and tetraalkylammonium fluoride.
• tetraalkylammonium hydroxide Preferred are tetraalkylammonium carbonate, tetraalkylammonium dicarbonate, and tetraalkylammonium fluoride, and more preferred are tetraalkylammonium hydroxide, tetraalkylammonium carbonate, and tetraalkylammonium dicarbonate. More preferred is tetraalkylammonium hydroxide.
• tetraalkylammonium hydroxide examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, benzyltrimethylammonium hydroxide, tetrabutylammonium hydroxide, phenyltrimethylammonium hydroxide, (C 5 H 11 ) 4 NOH, (C 16 H 33 ) (CH 3 ) 3 NOH, (C 16 H 33 ) (CH 3 ) 3 NOH, (C 8 H 17 ) 3 (CH 3 ) NOH, (C 8 H 17 ) 2 (C 10 H 21) (CH 3) NOH, (C 8 H 17) (C 10 H 21) 2 (CH 3) NOH, (C 10 H 21) 3 (CH 3) NOH, (C 8 H 17) 4 NOH, benzyltriethylammonium hydroxide and the like.
• tetraalkylammonium carbonate examples include tetramethylammonium carbonate, tetraethylammonium carbonate, tetrapropylammonium carbonate, benzyltrimethylammonium carbonate, tetrabutylammonium carbonate, and phenyltrimethylammonium hydroxide.
• tetraalkylammonium dicarbonate examples include tetramethylammonium bicarbonate, tetraethylammonium bicarbonate, tetrapropylammonium bicarbonate, benzyltrimethylammonium bicarbonate, tetrabutylammonium bicarbonate, and phenyltrimethylammonium bicarbonate.
• the amount of the base used is usually 0.5 mol to 100 mol, preferably 0.5 mol to 75 mol, more preferably 0.5 mol to 50 mol with respect to 1 mol of the total amount of raw material monomer components. is there.
• phase transfer catalyst examples include ammonium salt compounds, phosphonium salt compounds, macrocyclic polyethers, and the like, and ammonium salt compounds are preferable.
• a phase transfer catalyst may be used individually by 1 type, or may use 2 or more types together.
• ammonium salt compounds include tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrapentylammonium fluoride, tetrapentylammonium chloride, tetrapentylammonium bromide, and iodide.
• Tetrapentylammonium (C 16 H 33 ) (CH 3 ) 3 NCl, (C 8 H 17 ) 3 (CH 3 ) NCl, (C 8 H 17 ) 2 (C 10 H 21 ) (CH 3 ) NCl, ( C 8 H 17) (C 10 H 21) 2 (CH 3) NCl, (C 10 H 21) 3 (CH 3) NCl, (C 8 H 17) 4 NBr, benzyltriethylammonium chloride, and cetyl pyridinium chloride Among them, tetrabutylammonium bromide and tetrapentylammonium bromide are preferable.
• the amount of the phase transfer catalyst used is usually 0.001 mol to 50 mol, preferably 0.005 mol to 10 mol, more preferably 0.01 mol to 1 mol, based on 1 mol of the total amount of monomer components of the raw material. Is a mole.
• step (1) it is preferable to polymerize a monomer component including a monomer having a crosslinkable group after reducing the oxygen concentration in an inert gas atmosphere inside the reaction vessel.
• the oxygen concentration during the reaction is preferably 0.5% by volume or less, more preferably 0.2% by volume or less, and still more preferably 0.05% by volume or less.
• the reaction temperature is usually -100 ° C to 200 ° C, preferably 0 ° C to 150 ° C, more preferably 50 ° C to 100 ° C.
• the reaction time is usually 1 hour to 96 hours, preferably 2 hours to 48 hours.
• the reaction pressure is usually atmospheric pressure.
• the stirring power is usually 0.001kW / m 3 ⁇ 10kW / m 3, preferably 0.01kW / m 3 ⁇ 2kW / m 3.
• the raw material “monomer component containing a monomer having a crosslinkable group” used in the reaction of the step (1) includes a monomer having a crosslinkable group and, if necessary, a crosslinkable group. It means one or more monomers including other monomers not included.
• any of the “monomer components including a monomer having a crosslinkable group” preferably has two reactive groups capable of polymerization (coupling) in the molecule.
• the reactive group include X 1 and X 2 in the compounds represented by formula (1) and formula (2). These reactive groups are typical reactive groups used in the Suzuki coupling reaction.
• Crosslinkable group means a group capable of further crosslinking the polymer compound obtained by polymerizing the above “monomer component containing a monomer having a crosslinkable group” with heat, ultraviolet rays, or the like. To do.
• Examples of the “monomer component including a monomer having a crosslinkable group” include a compound represented by the formula (1) and a compound represented by the formula (2).
• the compound represented by the formula (1) and the compound represented by the formula (2) may each include one or more compounds (particularly 2 to 5 compounds). [Wherein, Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , X 1 , X 2 , a and b are the same as above] ]
• Ar 1 , Ar 2 , Ar 4 , and Ar 5 are each independently preferably a divalent aromatic hydrocarbon group or a group in which a divalent aromatic hydrocarbon group and a divalent heterocyclic group are bonded. These groups may have a substituent.
• the divalent aromatic hydrocarbon group represented by Ar 1 , Ar 2 , Ar 4 , and Ar 5 is preferably represented by formula (A-1), formula (A-6), formula (A-7), formula A group represented by formula (A-9) to formula (A-11) or formula (A-19), more preferably a group represented by formula (A-1) or formula (A-9) And more preferably a group represented by the formula (A-9).
• the divalent heterocyclic group represented by Ar 1 , Ar 2 , Ar 4 , and Ar 5 is preferably represented by formula (A-21), formula (A-22), formula (A-24) or formula (A -27) to a group represented by formula (A-46), more preferably a group represented by formula (A-21), formula (A-22) or formula (A-24).
• Examples of the group in which a divalent aromatic hydrocarbon group represented by Ar 1 , Ar 2 , Ar 4 , and Ar 5 and a divalent heterocyclic group are bonded include groups represented by the following formulae. These groups may have a substituent.
• Ar 3 and Ar 6 are each independently preferably a monovalent aromatic hydrocarbon group, and the group may have a substituent.
• a and b are each independently preferably an integer of 0 to 2, and more preferably 0 or 1.
• a or b is preferably 1 or 2.
• X 1 is preferably a bromine atom, an iodine atom, or —O—S ( ⁇ O) 2 R a1 (R a1 is the same as described above), and more preferably a bromine atom.
• Examples of the group represented by —O—S ( ⁇ O) 2 R a1 include a methanesulfonyloxy group, an ethanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a p-toluenesulfonyloxy group.
• Examples of the borane residue represented by X 2 include a group represented by the formula (G-1).
• Examples of the boric acid ester residue represented by X 2 include groups represented by formulas (G-2) to (G-11), and preferably the formula (G-4) or the formula (G A group represented by G-5).
• X 2 is preferably a borate ester residue.
• At least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 or Ar 6 has a group containing a crosslinkable group as a substituent.
• Ar 1 to Ar 6 those having a group containing a crosslinkable group are usually 1 to 5, preferably 1 to 3.
• each L is independently a single bond, or — (CH 2 ) —, —O—, —S—, — (CO) —, — (C 6 H 4 ) —, or these.
• Y represents a crosslinkable group.
• n represents an integer of 1 to 5.
• L for example, — (CH 2 ) m —, — (CH 2 ) p — (C 6 H 4 ) — (CH 2 ) q —, — (CH 2 ) r —O— (CH 2 ) s —, -(CH 2 ) t- (C 6 H 4 ) -O- (CH 2 ) u- and the like.
• m represents an integer of 0 to 20
• p represents an integer of 0 to 10
• q represents an integer of 0 to 10
• r represents an integer of 0 to 10
• s represents an integer of 0 to 10.
• T represents an integer of 0 to 10
• u represents an integer of 0 to 10.
• L is — (CH 2 ) m — (m is an integer of 0 to 10), — (CH 2 ) p — (C 6 H 4 ) — (CH 2 ) q — (p is an integer of 0 to 5, q is an integer of 0 to 10), and — (CH 2 ) r —O— (CH 2 ) s — (r is an integer of 0 to 5, and s is an integer of 0 to 10) is preferable.
• N is preferably an integer of 1 to 2, more preferably 1.
• the crosslinkable group represented by Y is not particularly limited as long as it is a group capable of crosslinking the polymer compound. Specifically, a group selected from the crosslinkable group group A is preferable. ⁇ Crosslinkable group A> (In the formula, each of these groups may have a substituent selected from the group consisting of an alkyl group and an aryl group.
• R XL is — (CH 2 ) —, —O—, —S—, — (CO) — or a divalent group in which two or more groups selected from these are bonded, provided that —O—, —S—, —O— and —S— are directly bonded to each other.
• N XL represents an integer of 0 to 5. When a plurality of R XL are present, they may be the same or different, and when a plurality of n XL are present, they may be the same or different. * Is a binding site with L.)
• formula (XL-1), formula (XL-7) to formula (XL-16), formula (XL-18), formula (XL-19), formula (XL-22) And a group represented by the formula (XL-23) are preferred, the formula (XL-1), the formula (XL-10), the formula (XL-12), the formula (XL-16), and the formula (XL-18). And a group represented by the formula (XL-19) are more preferable, a group represented by the formula (XL-1), the formula (XL-16), and the formula (XL-19) are more preferable, and the group represented by the formula (XL -1) and groups represented by the formula (XL-16) are particularly preferred.
• the monomer having a crosslinkable group have structures represented by the following formulas (2-1) to (2-31) and formulas (2′-1) to (2′-9).
• Compounds are preferred, and compounds having structures represented by the following formulas (2-1) to (2-30) and formulas (2′-1) to (2′-9) are preferred. These may have a substituent.
• These structures are represented as divalent groups obtained by removing the reactive groups (X 1 and X 2 ) from the compound represented by the formula (1) and the compound represented by the formula (2), respectively.
• the ratio of the monomer having a crosslinkable group in the total monomer components of the raw material is preferably 1 to 90 mol, more preferably 5 to 50 mol, relative to 100 mol of the total monomer components. More preferably, it is 8 to 25 mol.
• the ratio of the crosslinkable group in all the monomer components of the raw material is usually 1 to 180 mol, preferably 5 to 100 mol, more preferably 8 to 50 mol, relative to 100 mol of all monomer components. It is.
• the first polymer compound includes both a compound obtained by polymerizing only a monomer having a crosslinkable group, or a compound obtained by polymerizing a monomer having a crosslinkable group and another monomer. Among these, a compound obtained by polymerizing a monomer having a crosslinkable group and another monomer is preferable.
• Examples thereof include a polymer compound containing a unit and a structural unit represented by the formula (4).
• the first polymer compound includes, for example, one or more structural units represented by the formula (3), and one or more structural units represented by the formula (4). .
• the first polymer compound obtained in the step (1) generally contains a low molecular weight polymer depending on the polymerization (for example, Suzuki coupling reaction) conditions, and its polydispersity is also increased. There is a tendency.
• the polystyrene equivalent weight average molecular weight (Mw) of the first polymer compound is usually 3 ⁇ 10 4 to 3 ⁇ 10 5 , preferably 3 ⁇ 10 4 to 2 ⁇ 10 5.
• the degree of dispersion is usually 3 to 100, preferably 3 to 15.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw / Mn) can be measured and calculated according to the molecular weight analysis described in the examples.
• Step (2) includes adding a second solvent that is a poor solvent for the first polymer compound to a solution containing the first solvent and the first polymer compound, and then adding two or more layers. And separating a layer containing a polymer compound having the largest polystyrene-equivalent weight average molecular weight to obtain a second polymer compound having a crosslinkable group.
• the first solvent includes a solvent of the same type as the solvent used in step (1), and the solvent included in each of the two or more layers is substantially an organic solvent. .
• the first solvent contains the same type of solvent as used in step (1), and the solvent is preferably a solvent (good solvent) that can dissolve the first polymer compound.
• a solvent that is a good solvent for the first polymer compound can be selected from the solvents used in the step (1).
• the 1st solvent may be used individually by 1 type, may use 2 or more types together, and may contain water. Of these, aromatic hydrocarbon solvents and ether solvents are preferred, and aromatic hydrocarbon solvents are more preferred.
• the carbon number of the aromatic hydrocarbon solvent is preferably 6 to 12, and more preferably 7 to 9.
• the aromatic hydrocarbon solvent is preferably toluene, xylene and mesitylene.
• the ether solvent may be any of linear, branched and cyclic ether solvents, but is preferably a cyclic ether solvent.
• the ether solvent preferably has 4 to 7 carbon atoms.
• the ether solvent is preferably tetrahydrofuran.
• the solvent used in the step (1) is used as it is as the first solvent in the step (2).
• the first solvent is preferably substantially an organic solvent.
• the organic solvent is, for example, 80% by weight or more, and preferably 90% by weight or more. It is preferably 100% by weight.
• the amount of the first solvent used in the solution containing the first solvent and the first polymer compound used in the step (2) is 1 part by weight of the total amount of the first polymer compound. Usually, it is 10 to 1000 parts by weight, preferably 50 to 300 parts by weight.
• the solution containing the first solvent and the first polymer compound used in step (2) is preferably subjected to adsorption purification.
• the adsorbent used include alumina and silica gel.
• the impurities are removed by treating the first polymer compound with the adsorbent, and the fractionation operation (layer separation) in step (2) can be performed smoothly.
• the second solvent is a poor solvent for the first polymer compound.
• the second solvent can be selected from various solvents according to the characteristics of the first polymer compound.
• the first polymer compound can be defined as a solvent having a solubility (20 ° C.) of less than 1 g / 100 g.
• a 2nd solvent is a thing which can melt
• the second solvent can be selected and used as a poor solvent for the first polymer compound.
• a 2nd solvent may be used individually by 1 type, or may use 2 or more types together, and may contain water.
• Examples of the second solvent include amide solvents, alcohol solvents, ketone solvents, aliphatic hydrocarbon solvents, ester solvents, and nitrile solvents, and alcohol solvents are preferable.
• Examples of the amide solvent include N-methyl-2-pyrrolidone.
• As the alcohol solvent an alcohol solvent having 1 to 6 carbon atoms is preferable, and methanol, ethanol, and isopropanol are more preferable.
• As the ketone solvent a ketone solvent having 3 to 6 carbon atoms is preferable, and acetone and methyl ethyl ketone are more preferable.
• ester solvent an ester solvent having 3 to 6 carbon atoms is preferable, and methyl acetate and ethyl acetate are more preferable.
• methanol, ethanol, isopropanol, acetone, and ethyl acetate are preferable, and methanol is more preferable.
• the second solvent is preferably substantially an organic solvent.
• the organic solvent is preferably 80% by weight or more, more preferably 90% by weight or more, particularly 100% by weight. % Is preferred.
• step (2) the solution containing the first solvent and the first polymer compound and the second solvent are mixed and then stirred and allowed to stand to separate into two or more layers (liquid layers).
• the layer containing the polymer compound having the largest weight average molecular weight is selected.
• the 2nd high molecular compound which has a larger weight average molecular weight and has a crosslinkable group with small polydispersity is acquirable.
• the amount of the second solvent used is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, based on 100 parts by weight of the solution containing the first solvent and the first polymer compound having a crosslinkable group. Part by weight or more is more preferred, 1000 parts by weight or less is preferred, 800 parts by weight or less is more preferred, 500 parts by weight or less is further preferred, and 300 parts by weight or less is particularly preferred.
• the temperature of the solution when adding the second solvent is preferably ⁇ 30 ° C. or higher, more preferably 0 ° C. or higher, and further preferably 10 ° C. or higher. Moreover, 60 degrees C or less is preferable, 40 degrees C or less is more preferable, and 30 degrees C or less is further more preferable.
• the stirring power is usually 0.001kW / m 3 ⁇ 10kW / m 3, preferably 0.01kW / m 3 ⁇ 2kW / m 3, More preferably, it is 0.1 kW / m 3 to 1 kW / m 3 .
• the standing time for separating into two or more layers is usually 10 minutes or longer, preferably 1 hour to 48 hours, more preferably 1 hour to 24 hours.
• the standing temperature for separating into two or more layers is preferably ⁇ 30 ° C. or higher, more preferably 0 ° C. or higher, and further preferably 10 ° C. or higher. Moreover, 60 degrees C or less is preferable, 40 degrees C or less is more preferable, and 30 degrees C or less is further more preferable.
• step (2) it is important to separate into two or more layers (liquid layers). If a solid is precipitated here, a second polymer compound having a low polydispersity cannot be obtained (see, for example, Comparative Example 1). Therefore, the fractionation step of this step (2) is completely different from the crystallization step of mixing a solution in which a polymer compound is dissolved and a poor solvent to precipitate a solid.
• the operation of separating into two or more liquid layers can be performed by appropriately adjusting the types and amounts of the first solvent and the second solvent according to the characteristics of the first polymer compound.
• the total solvent contained in each layer is substantially an organic solvent.
• substantially means that 80% by weight or more, further 90% by weight or more, particularly 95% by weight or more of the total solvent contained in each layer is an organic solvent.
• the layers separated by the above operation are fractionated, the weight average molecular weight of the polymer compound contained in each layer is measured, and the layer containing the polymer compound having the largest weight average molecular weight is obtained.
• a layer containing a polymer compound having the largest weight average molecular weight tends to be separated into a lower layer, and a layer containing a polymer compound having a smaller weight average molecular weight tends to be separated into an upper layer. Therefore, usually, the desired second polymer compound can be obtained by separating the lower layer.
• step (2) the above fractionation operation can be repeated as necessary. Thereby, the second polymer compound having a lower polydispersity can be obtained.
• the second polymer compound obtained by the fractionation operation in the step (2) is basically represented by the structural unit represented by the formula (3) and the formula (4), like the first polymer compound. And a structural unit.
• the second high molecular compound since the low molecular weight compound is removed by the fractionation operation in the step (2), the second high molecular compound has a larger weight average molecular weight than the first high molecular compound and has a high molecular weight. The degree of dispersion has decreased dramatically.
• the polystyrene equivalent weight average molecular weight (Mw) of the second polymer compound is usually 7 ⁇ 10 4 to 6 ⁇ 10 6 , preferably 7 ⁇ 10 4 to 3 ⁇ 10 5 , more preferably 1 ⁇ a 10 5 ⁇ 3 ⁇ 10 5, the polydispersity (Mw / Mn) is usually 1 to 20, preferably 1 to 3, more preferably 1.1 to 2.5.
• steps (1) and (2) may be continuous steps, or other steps may be provided between both steps. Further, another step may be provided after step (2). Examples of other steps include a terminal blocking step, a liquid separation step, an azeotropic dehydration step, a purification step and the like of the first polymer compound obtained in step (1).
• a monofunctional compound is added to the reaction solution, and the first polymer This is a step of sealing (substituting) a reactive terminal group in a compound with a monofunctional compound.
• the elongation of the molecular weight of the first polymer compound is stopped means that when the weight average molecular weight is measured at intervals of 30 minutes during the reaction, the change in the weight average molecular weight is 3 It means the state that became less than%.
• a weight average molecular weight can be measured using the method as described in an Example.
• X 1 includes a halogen atom (chlorine atom, bromine atom, iodine atom, etc.), —O—S ( ⁇ O) 2 R a1
• X 2 represents —B (OH) 2 , borane residue, borate ester residue, —BF 3 T (wherein R a1 and T are the same as above).
• Examples of the monofunctional compound to be added include compounds having one reactive group capable of sealing the reactive terminal group of the first polymer compound by the Suzuki coupling reaction.
• the reactive end groups of the first polymer compound is X 1
• monofunctional compound is a compound having one reactive group X 2
• reactive end groups of the first polymer compound X 2 In this case, the monofunctional compound is a compound having one reactive group X1.
• Specific examples of the monofunctional compound include a compound in which the reactive group X 1 or X 2 and an aryl group are bonded, a compound in which the reactive group X 1 or X 2 and a heterocyclic group are bonded, and the like. More specifically, phenylboronic acid, phenyl bromide and the like can be mentioned.
• a monofunctional compound, an aryl group or a monovalent compounds with reactive groups X 1 or X 2 is bonded to the heterocyclic group having a crosslinkable group selected from the aforementioned crosslinkable group group A, the formula (XL -16) and a compound in which the reactive group X 1 or X 2 is bonded.
• the desired reactive terminal group was sealed by fractionating by the same operation as said process (2).
• a second polymer compound can be obtained.
• the reaction solution containing the first polymer compound is mixed with at least one of an acidic aqueous solution such as hydrochloric acid, a basic aqueous solution such as an aqueous ammonia solution, water, saline, and the like.
• an acidic aqueous solution such as hydrochloric acid
• a basic aqueous solution such as an aqueous ammonia solution
• water, saline, and the like This is a step of separating the layers and obtaining an organic layer containing the desired first polymer compound.
• This step is a step of extracting and washing the organic substance containing the first polymer compound from the reaction solution.
• Step (2) of the present invention that is, removing the low molecular weight compound to obtain the desired second polymer. It should be noted that this is completely different from the fractionation process to obtain the compound.
• the azeotropic dehydration step is a step of azeotropic dehydration of the solution containing the first polymer compound at normal pressure or while reducing the pressure.
• the purification step includes, for example, reprecipitation, continuous extraction with a Soxhlet extractor, a step of purification by column chromatography, a crystallization step, an adsorption purification (step of treating with an adsorbent), and the like.
• This purification step can be carried out using any known method.
• This purification step may be provided after step (2).
• step (1) / end capping step / separation step / dehydration step / column chromatography step / "Step (2)”, “Step (1)” / End-blocking step / Separation step / Column chromatography step / "Step (2)”, “Step (1)” / End-blocking step / Separation step / "Process (2)” etc. are mentioned.
• the obtained toluene solution was adsorbed and purified by passing through a column in which alumina and silica gel were mixed to obtain 1000.2 g of a toluene solution of the first polymer compound (P1).
• the first polymer compound (P1) had Mn of 2.8 ⁇ 10 4 , Mw of 9.6 ⁇ 10 4 , and polydispersity of 3.4.
• Step (2) To a toluene solution (553.7 g) of the obtained first polymer compound (P1), methanol (149.5 g) (27 parts by weight of methanol with respect to 100 parts by weight of toluene solution) was stirred at a power of 0.3 kW / m 3. Dropped and stirred for 1 hour. The obtained mixture was allowed to stand at 22 ° C. for 17.5 hours to separate into two layers, and the lower layer having a large polystyrene-equivalent weight average molecular weight was separated. The fractionated lower layer was diluted with toluene (310.5 g) to obtain a second polymer compound (P2).
• the second polymer compound (P2) had Mn of 6.1 ⁇ 10 4 , Mw of 1.3 ⁇ 10 5 , and polydispersity of 2.1.
• a toluene solution of the obtained second polymer compound (P2) was added dropwise to methanol (2117 g) and stirred for 1 hour, and then the resulting solid was collected by filtration and dried to obtain a polymer compound (P3). It was.
• the polymer compound (P3) had an Mn of 6.3 ⁇ 10 4 , an Mw of 1.3 ⁇ 10 5 , and a polydispersity of 2.1.
• Example 2 [Fractionation step: Step (2)] To 100 parts by weight of the toluene solution of the first polymer compound (P1) obtained in the column step of Example 1, 39 parts by weight of ethanol was added dropwise and stirred. The obtained mixture was allowed to stand at 23 ° C. for 2.5 hours to separate into two layers, and the lower layer having a large polystyrene-equivalent weight average molecular weight was separated. The fractionated lower layer was diluted with toluene to obtain a second polymer compound (P4).
• the polymer compound (P4) had Mn of 8.8 ⁇ 10 4 , Mw of 1.7 ⁇ 10 5 , and polydispersity of 2.0.
• the crude product of the first polymer compound had Mn of 1.2 ⁇ 10 4 , Mw of 1.0 ⁇ 10 5 , and polydispersity of 8.4.
• the obtained xylene solution was subjected to adsorption purification by passing through a column in which alumina and silica gel were mixed to obtain a xylene solution of the first polymer compound (P9).
• the polymer compound (P9) had Mn of 1.1 ⁇ 10 4 , Mw of 9.9 ⁇ 10 4 , and polydispersity of 8.7.
• Step (2) To 100 parts by weight of the obtained first polymer compound (P9) in xylene, 24 parts by weight of methanol was added dropwise and stirred at 23 ° C. The obtained mixture was allowed to stand at 23 ° C. for 1.5 hours to separate into two layers, and the lower layer having a large polystyrene-equivalent weight average molecular weight was separated. The fractionated lower layer was diluted with xylene to obtain a second polymer compound (P10).
• the second polymer compound (P10) had an Mn of 5.3 ⁇ 10 4 , an Mw of 1.2 ⁇ 10 5 , and a polydispersity of 2.3.
• Example 7 [Fractionation step: Step (2)] 40 parts by weight of ethanol was added dropwise to 100 parts by weight of the xylene solution of the first polymer compound (P9) obtained in the column step of Example 6 and stirred, and then allowed to stand at 23 ° C. for 1.5 hours. Separated into two layers, the lower layer having a large polystyrene-equivalent weight average molecular weight was separated and diluted with xylene to obtain a second polymer compound (P11).
• the polymer compound (P11) had an Mn of 5.1 ⁇ 10 4 , an Mw of 1.2 ⁇ 10 5 , and a polydispersity of 2.3.
• Example 9 [Fractionation step: Step (2)] 65 parts by weight of acetone was added dropwise to 100 parts by weight of the xylene solution of the first polymer compound (P9) obtained in the column step of Example 6 and stirred. The obtained mixture was allowed to stand at 23 ° C. for 2 hours to separate into two layers, and the lower layer having a large polystyrene-equivalent weight average molecular weight was separated. The fractionated lower layer was diluted with xylene to obtain a second polymer compound (P13).
• the polymer compound (P13) had an Mn of 7.2 ⁇ 10 4 , an Mw of 1.8 ⁇ 10 5 , and a polydispersity of 2.5.
• Example 12 [Fractionation step: Step (2)] 24 parts by weight of methanol was added dropwise to 100 parts by weight of the xylene solution of the first polymer compound (P9) obtained in the column step of Example 6 and stirred. The obtained mixture was allowed to stand at 10 ° C. for 3 hours and separated into two layers, and the lower layer having a large polystyrene-equivalent weight average molecular weight was separated. The fractionated lower layer was diluted with xylene to obtain a second polymer compound (P16).
• the polymer compound (P16) had Mn of 5.0 ⁇ 10 4 , Mw of 1.2 ⁇ 10 5 , and polydispersity of 2.4.
• the obtained mixed solution of tetrahydrofuran and toluene was adsorbed and purified by passing through a column mixed with alumina and silica gel to obtain 282.8 g of a mixed solution of first polymer compound (P18) in tetrahydrofuran and toluene.
• the first polymer compound (P18) had Mn of 4.4 ⁇ 10 3 , Mw of 2.7 ⁇ 10 5 , and polydispersity of 61.3.
• Step (2) 20 parts by weight of methanol was added dropwise to 100 parts by weight of a mixed solution of tetrahydrofuran and toluene of the obtained first polymer compound (P18) and stirred. The obtained mixture was allowed to stand at 23 ° C. for 1.5 hours to separate into two layers, and the lower layer having a large polystyrene-equivalent weight average molecular weight was separated. The fractionated lower layer was diluted with toluene to obtain a second polymer compound (P19).
• the second polymer compound (P19) had Mn of 2.4 ⁇ 10 4 , Mw of 3.4 ⁇ 10 5 , and polydispersity of 13.9.
• Example 15 [Fractionation step: Step (2)] 16 parts by weight of methanol was added dropwise to 100 parts by weight of a mixed solution of tetrahydrofuran and toluene of the first polymer compound (P18) obtained in the column step of Example 14, and stirred. The obtained mixture was allowed to stand at 23 ° C. for 1.5 hours to separate into two layers, and the lower layer having a large polystyrene-equivalent weight average molecular weight was separated. The separated lower layer was diluted with toluene to obtain a second polymer compound (P20).
• the second polymer compound (P20) had Mn of 2.8 ⁇ 10 4 , Mw of 5.3 ⁇ 10 5 , and polydispersity of 18.9.

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